Cellulose-Chitin Composites for Performance Advantaged ...
Transcript of Cellulose-Chitin Composites for Performance Advantaged ...
DOE Bioenergy Technologies Office (BETO)
2021 Project Peer Review
Cellulose-Chitin Composites for Performance
Advantaged Barrier Products
March 10, 2021
Technology Area Session
Carson Meredith
Georgia Tech
This presentation does not contain any proprietary, confidential, or otherwise restricted information
Project Overview
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What: Develop a performance advantaged bioproduct (PABP)
alternative to petroleum-based flexible packaging
How: Scalable coating biomass-based multilayer films with at
least 10% improvement in O2 permeability vs. PET
State-of-art: multilayer flexible packaging
-critical to food safety & supply
-multimaterial petroleum derived
-unrecyclable/nondegradable
Why - Impact:
-valuable by-products from biorefineries
-reduced landfill use and ocean leakage
-circular packaging alternative – reuse of carbon
Risks: cost to produce, achieving performance advantage in
manufacturable format, biomass availability
DE‐FOA‐0001916
Topic 3: PABP
packworld.com
1 – Management
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Task 1: Initial Verification (M1-M3) → GNG
Task 2: PABP Design and Prototyping (M4-M18) → GNG
Task 3: PABP Optimization for Food and Device Packaging (M19-36)
Task 4: PABP Manufacturability (M19-36)
C. Meredith (ChBE): chitin extraction, spray coat, transport props., TEA
M. Shofner (MSE): mechanical properties & rheology
T. Harris (ME): interface properties & slot die coating
J. Reynolds (CHEM): electrochromic device packaging & testing
1 – Management
Year 1 – bi-weekly meetings whole team; weekly subteam meetings
Year 2/3 – tri-weekly whole team; weekly subteams
Whole team meetings focus on interdisciplinary feedback, data and material
exchange, and maintaining focus on task objectives
Changes in student or post-doc staffing are discussed and agreed by PI/coPIs
Challenges in student/post-doc performance handled by PI and CoPI involved
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1 – ManagementIndustrial stakeholder engagement
Tidal Vision – Chitin producer in North America
Sugino – Japan-based chitin nanofiber producer
Winpak, Ltd. – N.A. flexible packaging converter – evaluation of
material for commercial coating.
Nestle – global food brand – selection of compatible products
Collaboration
Georgia Tech RBI-funded project overlap
NREL Peter Ciesielski – SEM EDS profiling for concentration profiles
UGA Jason Locklin – biodegradation trial underway
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evaluation of commercially
available materials
1 – Management
Risk Mitigation
Compatibility with converters Focus on scalable coating technology
available to converters
Feedstock availability cellulose: 137 million tons annual
chitin: 3-6 million tons annual
Process costs Process design and optimization
Mechanical properties/durability Subtask dedicated to optimization and
durability testing
Biodegradability / compostability Trial with University of Georgia facility
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1 µm 7
2 – Approach
Biomass sources with potential to exceed oxygen barrier properties of PET
Cellulose Nanocrystals
(CNCs)
Wood/Plant
Crustacean food waste/
Fungi
Exploit synergism between chitin and
cellulose-based nanofibers
CNC
(-ve)
+
+ +
+ +
++
ChNF
(+ve)
Achieve barrier performance,
mechanical and optical properties
- - - - - - - - - -
- - - -+ + + + + + + + + + +
+ + - - - - - - - - - -
- - - -
Cellulose NC
Chitin NF
Cellulose NC
Produce dense, well-adhered
interfaces through layeringChitin Nanofibers
(ChNFs)
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2 – ApproachChallenges
-Proposal baseline was spray-coated with OP 2.5x > PET
-Manufacturing in single coating pass by dual-layer slot-die
-Achieving O2 Permeability (OP) below PET with manufacturable process
-Sensitivity of OP to drying environment humidity
-Water vapor sensitivity of OP
-Mechanical properties
-Cost of ChNF production
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2 – Approach
GNG 1 – Initial Verification at Month 3 (January 2019)
Established capability to produce adequate supply of material
Established baseline for benchmark PET and for starting point of bilayer coatings on
new substrate, cellulose acetate (CA)
Identified critical hand-offs in information and materials amongst coPIs
GNG 2 – Intermediate Verification at Month 18 (July 2020)
Verification of PABP OP 10% improvement versus PET
Identification of challenges to reproducibility
Identification of project priorities for budget period 3 (final 18 months)
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2 – Approach
Technical Metrics
-O2 Permeability (OP) – normalized barrier performance,
measured at room T and 50% relative humidity
-Water vapor transport rate (WVTR)
-Puncture strength, Elongation at break
-Electrochromic device performance
(switching time, photostability)
Economic Metrics
-First-pass process design
-cost per kg to produce ChNFs
exploring pulp mill integration
-energy utilization per kg ChNF
-cost and energy per m2 to coat and dry
3 – Impact
Our PABP is a biomass-derived, degradable alternative to current unrecyclable /
nondegradable flexible packaging → about 1 trillion units of plastic waste per year
CNCs and chitin are biodegradable → a solution for food packaging to biodegrade or compost
with waste food.
Circular return of CO2 back to biomass production – carbon regeneration
Addresses landfill use, environmental leakage (oceans) and microplastic accumulation
Meets industry-driven demand for alternative single-use plastic package designs.
re: New Plastics Economy Global Commitment 12
https://ourworldindata.org/faq-on-plastics
3 – Impact
Publications
1 article in ACS Sustainable Chem. & Eng. (IF=7.6)
1 article in Emergent Materials (no IF)
2 articles in preparation
ACS Sustainable Chemistry & Engineering (IF = 7.6)
ACS Applied Materials & Interfaces (IF = 8.76)
Commercialization Developments
Proposal to USDA/US Endowment for Forests for commercialization with Mars, Inc.
Piloting project with a major packaging converter to explore adaptation to other
commercial coating operations.
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ASAP 2021 doi.org/10.1021/acssuschemeng.0c09121
Emergent Materials 3 919–936 (2020)
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4 – Progress and Outcomes
Actual Completion
31-Mar-19
1-Aug-20
1-Aug-20
1-Mar-20
31-Dec-19
1-Aug-20
1-Aug-20
4.2 Cost estimation for chitin-cellulose PABP production 31-Dec-21 10%
4.3 Final Verification and Reporting 31-Dec-21 0%
4.1 Implement multilayer slot die processing 31-Dec-21 20%
4 PABP Manufacturability 31-Dec-21 15%
3.3 Optical property optimization 30-Jun-21 10%
3.4 Apply PABP to electrochromic display packaging 31-Dec-21 20%
3.2 Mechanical property optimization 30-Jun-21 20%
3 Optimization for food and device packaging 31-Dec-21 20%
3.1 Barrier property optimization 30-Jun-21 30%
2.5 Intermediate verification task 30-Jun-20 100%
2.4 Produce slot-coated PABPs / characterize barrier 30-Jun-20 100%
2.3 Lab-scale exploration of PABP design and composition 31-Dec-19 100%
2.2 Optimization of suspensions for single layer slot die 1-Mar-20 100%
2.1 Chitin and cellulse stock material production 30-Jun-20 100%
1 Initial Verification 31-Mar-19 100%
2 PABP Design and Prototyping 30-Jun-20 100%
Task Description Planned Completion % Complete
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4 – Progress and Outcomes
Subtask 2.1 – Supply CNC and ChNF
suspensions via biomass extraction
Subtask 2.3 - Lab-scale exploration of
PABP design and composition
We discovered that the ChNFs can
be optimized through their extraction
processing.
The resulting fiber size and charge
leads to widely different performance
in a bilayer coated with CNCs.
Sprayed ChNF + CNC on
cellulose acetate (CA)
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68
55
44
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5244
32
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Or1
-1
Or1
-2
Or1
-3
Or1
-4
Or1
-5
Or1
-6
Or1
-7
Or1
-8
Or1
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Or1
-opt
Or1
-har
sh
0
50
100
150
OP
(cc-
m/m
2/d
ay/k
Pa
)
ChNF
ChNF process intensity
→changes to size and charge
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Or1-1Or1-2
Or1-3Or1-4
Or1-5Or1-6
Or1-7Or1-8
Or1-9
Or1-opt
Or1-harsh0
50
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OP (c
c-m/
m2 /day/k
Pa)
ChNF
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chitosan
additive
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4 – Progress and Outcomes
Subtask 2.4 – Produce slot-coated PABPs
Subtask 4.1 – Optimize dual-layer slot-die
Dual-chamber slot die produced.
Films with OP values from
1.7 to 7.2 cm3m m-2d-1kP-1
produced, depending on conditions.
Exceeds GNG target of 9 cm3m m-2d-1kP-1.
The ‘best’ oriented PET on the market is
10 cm3m m-2d-1kP-1.
GNG
slot layered
0.00001
0.0001
0.001
0.01
0.1
1
10
Ox
yg
en
Perm
ea
bilit
y
(cm
3
m/m
2/d
ay/K
Pa)
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4 – Progress and Outcomes
Subtask 2.3 – Encapsulation of ECDs
Subtask 3.4 – ECD packaging optimization
Performance of ECDs packaged in
CNC/ChNF/CA barriers is near 3M FTB
and better than PET.
Glass
ITO
ECP-EH
Glass or Barrier
Film
Organic
Electrolyte
In situ PEDOT
Photostability
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4 – Progress and Outcomes
Actual Completion
30-Jun-19
30-Jun-19
30-Sep-19
31-Dec-19
31-Mar-20
30-Jun-20
17-Aug-20
31-Dec-20
31-Dec-20
DescriptionMilestone Planned Completion % Complete
0%4.3.ML.1 Verification of final performance for PABP 31-Dec-21
4.1.ML.1 Fabricate bilayer or multilayer PABP on CA with multilayer 31-Dec-20
10%3.4.ML.3 Attain increase in bleaching time with PABP 30-Sep-21
3.4.ML.2 Achieve optical performance with PABP coating intact 31-Mar-21
100%3.4.ML.1 Identify gel electrolyte with acceptable performance 30-Sep-20
3.2.ML.1 Determine process conditions that optimize mechanical 30-Jun-21
2.5.ML.2 PABP films have at least 10% PO2 improvement 30-Jun-20
100%2.5.ML.1 Chitin-cellulose PABP produced with 10% PO2 30-Jun-20
100%2.4.ML.1 Design multilayer slot die 31-Mar-20
100%2.3.ML.1 Produce spray-dried prototypes and report O2 31-Dec-19
100%2.2.ML.2 Measure rheological properties / lower boundary limit 30-Sep-19
2.2.ML.1 Measure wetting properties of suspensions from 2.1 3-Jun-19
2.1.ML.1 Production of required quantities of ChNF and CNC 30-Jun-19
100%
50%
10%
100%
100%
100%
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Summary
• This project is developing a performance advantaged bioproduct
-biomass alternative to petroleum products utilized in flexible packaging for oxygen barriers
-intermediate target 10% reduction in O2 permeability vs. PET
-final target 80% reduction in O2 permeability vs. PET
• Focus on manufacturable approach by slot-die coating → simultaneous deposition of chitin-
cellulose nanomaterial bilayers
• We have achieved a 28% to 83% reduction in O2 permeability reduction relative to biaxially
oriented PET film
• Impact: expands range of byproducts of biomass biorefining; reduces landfill; regenerates
carbon in packaging (#1 source of plastic waste)
• Final year in project is focusing on optimization of O2 permeability, effects of humidity,
mechanical properties, process design and cost analysis.
Quad Chart Overview (Competitive Project)
Timeline• 10/1/2018
• 3/31/2022
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FY20
CostedTotal Award
DOE Funding
$334,012 $1,015,501
Project
Cost
Share
$70,614 $285,075
Project GoalThis project will produce a performance advantaged bioproduct for flexible plastic food and electronics packaging, formed from biomass sources, which exceeds the O2 barrier performance of oriented poly(ethylene terephthalate)(PET) by 10% to 500%.
End of Project Milestone
Project Partners*
N/A
Funding MechanismBEEPS DE-FOA-0001916
Topic 3
2018
*Only fill out if applicable.
Oxygen Permeability 2 cm3 m / (m2 kPa d)
Water Vapor
Transmission Rate 1 g mm/(m2 d)
Puncture strength 50 Mpa
Strain % at break 35 %
Light Transmission 90 %
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Responses to Previous Reviewers’ Comments
• Highlights from Initial Verification Go/No-Go Review
– Encouragement to carry out experimental design
• Our team carried out a design of experiments on ChNF preparation, exploring a 3-
factorial design and discovering an optimal preparation of ChNFs minimizing OP
– Focus on solving difficulties spray-coating cellulose acetate (CA) and
establish a new project baseline for CNC/ChNF/CA coated films.
• Issues faced at verification visit with CA deformation during spraying were resolved
shortly afterwards. A new baseline was established.
– The project would benefit from more detailed discussions of key parameters
constituting the “design” that will be handed-off from the spray coating work
to the slot die coating work.
• Parameters affecting suspension coatability was defined collaboratively by the spray-
and slot-die teams and tracked for all batches of suspension that were developed.
– An industrially relevant PET benchmark should be identified and measured
in the lab, instead of relying on literature values.
• Oriented PET (lowest O2 permeability available) was obtained from a leading
manufacturer and measured in the PI’s lab as a benchmark.
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Responses to Previous Reviewers’ Comments
• Highlights from Intermediate (M18) Verification Go/No-Go Review
– Alterative film thickness measurement method recommented
• Interferometry instrument identified, budget rearranged to allow its purchase. It
is now installed.
– Explore potential use of alcohol as co-solvent in drying
• Currently under exploration. Recent literature reviewed on use of alkylated
chitosans to improve dispersion in alcohols.
– Consider a visit to NREL with trial on coating and drying line
• To be considered when travel restrictions lift.
– In TEA work be sure to consider side product valuation
• Protein and mineral side products to be considered in TEA.
– Focus on lessons learned from drying protocol
• Deeper study ongoing to evaluate drying variables, water content and O2
permeability response
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Publications, Patents, Presentations,
Awards, and Commercialization
• Publications
1. Lang, Y. Ji, A. Dillon, C. Satam, J.C. Meredith, J. Reynolds*, “Photostability of Ambient-Processed, Conjugated-Polymer Electrochromic Devices
Encapsulated by Bioderived Barrier Films,” ACS Sustainable Chemistry and Engineering, 2021, in press.
2. Z. Yu, Y. Ji, V, Bourg, M. Bilgen, J.C. Meredith*, “Chitin- and Cellulose-Based Sustainable Barrier Materials: A Review,” Emergent Materials, 2020, 3, 919–
936 https://doi.org/10.1007/s42247-020-00147-5
• Presentations
1. AIChE Sustainable Packaging Symposium, July 2020
2. Energy and Fuels Renewability Symposium, ACS Spring National Meeting 2020
3. University of Florida Dept. of Chemical Engineering Symposium, March 9, 2020
4. Frontiers of Green Materials, December 16, 2019, London.
5. Workshop on Polymers for a Circular Economy, DOE BETO, Golden, CO, December 11, 2019
6. 4th International Symposium on Materials from Renewables, University of Georgia, October 9-10, 2019, Athens, GA.
7. Biodegradable Environmental Polymer Society, June 5-7, 2019, Clemson, SC.
8. SKC Corporation, May 2019, Covington, GA.
9. ACS Bioinspired Polymer Session, April 4, 2019 ACS Spring National Meeting, Orlando, FL.
• Commercialization efforts
– USDA/US Endowment for Forests P3Nano Proposal submission for commercialization with partner Mars, Inc. (submitted Feb 2, 2021)
– Tech transfer with a food brand / converter partnership to explore other coating methods